Hochberg David, Bourdon García Rubén D, Ágreda Bastidas Jesús A, Ribó Josep M
Department of Molecular Evolution, Centro de Astrobiología (CSIC-INTA), Carretera Ajalvir Kilómetro 4, 28850 Torrejón de Ardoz, Madrid, Spain.
Department of Chemistry, Universidad Nacional de Colombia, Bogotá, Colombia.
Phys Chem Chem Phys. 2017 Jul 21;19(27):17618-17636. doi: 10.1039/c7cp02159c. Epub 2017 Jun 30.
We apply stoichiometric network analysis (SNA) to study enantioselective chemical reaction schemes, subject to various thermodynamic architectures, which may lead to spontaneous mirror symmetry breaking (SMSB). Stoichiometric matrices are used to calculate extreme currents or fluxes: the vector basis for the convex polyhedral cone of all stationary reaction rates. A major emphasis is given to the constraints that the rate constants must obey and how to express these in terms of the convex parameters and stationary inverse concentrations. We evaluate the corresponding Jacobians in terms of the constrained convex parameters and the inverse stationary concentrations and carry out stability analyses for the steady-state racemic configurations. A geometric visualization of SMSB is proposed, based on the structures of the convex cones, the angles between currents, and the cone's subspaces that result from enforcing the pertinent thermodynamic and chiral constraints.
我们应用化学计量网络分析（SNA）来研究对映选择性化学反应方案，这些方案受各种热力学结构的影响，这可能导致自发的镜像对称性破缺（SMSB）。化学计量矩阵用于计算极限电流或通量：所有稳态反应速率的凸多面锥的向量基。主要强调速率常数必须遵守的约束条件，以及如何用凸参数和稳态逆浓度来表示这些约束条件。我们根据受约束的凸参数和稳态逆浓度来评估相应的雅可比矩阵，并对稳态外消旋构型进行稳定性分析。基于凸锥的结构、电流之间的夹角以及由于实施相关热力学和手性约束而产生的锥子空间，提出了一种SMSB的几何可视化方法。
